CN112661195B - Preparation method of subminiature magnetic ferroferric oxide nanoparticles - Google Patents
Preparation method of subminiature magnetic ferroferric oxide nanoparticles Download PDFInfo
- Publication number
- CN112661195B CN112661195B CN202011538513.XA CN202011538513A CN112661195B CN 112661195 B CN112661195 B CN 112661195B CN 202011538513 A CN202011538513 A CN 202011538513A CN 112661195 B CN112661195 B CN 112661195B
- Authority
- CN
- China
- Prior art keywords
- ferroferric oxide
- oxide nanoparticles
- magnetic ferroferric
- subminiature
- ferrihydrite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Compounds Of Iron (AREA)
Abstract
A preparation method of subminiature magnetic ferroferric oxide nanoparticles with the size less than 8nm relates to the technical field of nano material preparation. In order to overcome the defect that the nucleation and growth processes of the subminiature magnetic ferroferric oxide nanoparticles prepared by the existing method are difficult to control, ferrihydrite with a nano structure is used as a precursor, and the subminiature magnetic ferroferric oxide nanoparticles with uniform size, controllable particle size, good crystallinity, high purity and easy water solubility are obtained by heating reaction in polyhydric alcohol. The preparation method comprises the following steps: 1) ferric salt and alkaline substances are reacted in aqueous solution to obtain ferrihydrite precipitate; 2) and mixing the ferrihydrite precipitate with polyhydric alcohol and heating to obtain the ultra-small magnetic ferroferric oxide nano particles. The method has the advantages of easily available raw materials, low cost, simple process and suitability for large-scale production, and the obtained subminiature magnetic ferroferric oxide nanoparticles have wide application in the field of biomedicine.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a preparation method of a subminiature magnetic ferroferric oxide nano particle.
Background
The magnetic ferroferric oxide nano particle has unique magnetic property and good biocompatibility, and has wide application in the biomedical fields of cell separation, targeted drug delivery, gene delivery, Magnetic Resonance Imaging (MRI), tumor magnetic thermotherapy and the like. The magnetic performance and biological effect of the ferroferric oxide nano particles are closely related to the size and surface structure of the particles, and the preparation of the magnetic ferroferric oxide nano particles with different sizes and surface structures is a necessary condition for realizing various biomedical applications. Recent studies show that the subminiature magnetic ferroferric oxide nano-particles with the size less than 8nm have good T 1 The performance of magnetic resonance imaging has great potential in clinical diagnosis and therapy, and thus has attracted extensive research interest. The prior chemical synthesis method of the subminiature magnetic ferroferric oxide nano-particles mainly comprises a coprecipitation method, a high-temperature thermal decomposition method, a hydrothermal (solvent) thermal method and the like. Most of these methods are based on simple inorganic or organic iron-containing compoundsThe materials are subjected to hydrolysis, thermal decomposition, condensation and other reactions in the solution to gradually nucleate and grow to form the ferroferric oxide nano particles. Due to the complex reaction process, nucleation and growth are difficult to control effectively, and the obtained product has the defects of wide size distribution, more impurity phases, poor crystallinity, easy agglomeration and the like. Even if the nucleation and growth processes of the nanoparticles can be controlled to a certain degree by means of adding surfactants and the like, the hydrophobic surfactants are remained in the product and are difficult to remove, and the hydrophilicity and the biocompatibility of the nanoparticles are influenced.
The ferrihydrite is a weakly crystalline spherical iron hydroxide particle with a particle size of about 2-6nm and is Fe 3+ The first precipitation products of the hydrolysis process are widely distributed in water, soil, sediments and organisms. Ferrihydrite is unstable and is readily converted to more stable iron oxides or oxyhydroxides. But in the conversion process, the product is difficult to maintain the original nanometer size and shape of the ferrihydrite. The report of preparing the subminiature magnetic ferroferric oxide nano particles by using ferrihydrite as a precursor is not found yet after domestic and foreign documents are searched.
Disclosure of Invention
Aiming at the problem that the nucleation and growth processes are difficult to control in the reported preparation method of the subminiature magnetic ferroferric oxide nanoparticles, the invention provides a preparation method of the subminiature magnetic ferroferric oxide nanoparticles. The method comprises the steps of firstly preparing simple trivalent ferric salt into ferrihydrite with a nano structure, then taking the ferrihydrite as a precursor, and preparing the subminiature magnetic ferroferric oxide nano particles which are uniform in size, controllable in particle size, good in crystallinity, high in purity and easy to dissolve in water through heating reaction of the ferrihydrite in polyhydric alcohol. The method overcomes the problem of difficult control of nucleation and growth process in the existing preparation method, can realize large-scale production, and has wide application in the biomedical field.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing subminiature magnetic ferroferric oxide nanoparticles by taking ferrihydrite as a precursor comprises the following steps:
(1) ferric salt and alkaline substances are reacted in aqueous solution to obtain ferrihydrite precipitate;
(2) and (2) mixing the ferrihydrite precipitate obtained in the step (1) with polyol and heating to obtain the ultra-small magnetic ferroferric oxide nanoparticles.
Wherein the ferric iron salt in the step (1) is any one of ferric chloride, ferric nitrate and ferric sulfate; the alkaline substance is any one of sodium hydroxide, potassium hydroxide, ammonia water, ammonia gas, sodium carbonate, sodium bicarbonate and sodium acetate. The polyalcohol in the step (2) is any one of ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol with molecular weight less than 1000 daltons or a mixture thereof; the heating temperature is 130 ℃ to the boiling point of the solution; the reaction time is 10 minutes to 24 hours; the size of the obtained subminiature magnetic ferroferric oxide nano particles is less than 8 nm.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, cheap and easily-obtained trivalent ferric salt is firstly hydrolyzed to prepare ferrihydrite with a nano structure, and the ferrihydrite is heated and reacted in polyhydric alcohol to obtain the subminiature magnetic ferroferric oxide nano particles with uniform size, controllable particle size, good crystallinity, high purity and easy water solubility.
The ferrihydrite is 2-6nm weak crystalline iron hydroxide spherical particles and is composed of a core with high crystallinity and a shell with poor crystallinity. A part of the ferrihydrite is dissolved in the polyhydric alcohol and reduced to Fe 2+ And the other part is Fe adsorbed by 2+ Solid phase is converted into ferroferric oxide crystal nucleus and Fe in the solution is consumed 3+ And Fe 2+ Gradually growing into ferroferric oxide nano particles. As no new crystal nucleus is generated in the solution in the growth process any more, all the crystal nuclei grow under the same condition, the defect that the nucleation and growth processes are difficult to control in the prior art is overcome, and the nano particles with uniform size are finally obtained. It is also possible to obtain nanoparticles of different sizes by controlling the reaction time.
The boiling point temperature of the polyalcohol solvent is higher than that of water phase synthesis, so that the obtained ferroferric oxide nanoparticlesGood seed crystallinity and high saturation magnetization, and is beneficial to biomedical application. The polyol has reducing effect and can regulate Fe in solution 2+ The concentration of the ferroferric oxide nano particles is higher. The polyhydric alcohol can be adsorbed on the surface of the ferroferric oxide nano particles to prevent agglomeration among the nano particles, and the nano particles are endowed with good water solubility.
The preparation method of the subminiature magnetic tetraoxide nanoparticles provided by the invention has the advantages of low raw material cost, simple process and easiness in control, and is suitable for large-scale production.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of ferrihydrite obtained in example 1.
Fig. 2 is a Transmission Electron Microscope (TEM) image of the subminiature magnetic ferroferric oxide nanoparticles obtained in example 1, and the inset is a High Resolution TEM (HRTEM) image.
FIG. 3 is a comparison of X-ray diffraction (XRD) patterns of the subminiature magnetic ferroferric oxide nanoparticles obtained in example 1 with JCPDS65-3017 standard cards.
FIG. 4 is a room temperature magnetization curve of the ultra-small magnetic ferroferric oxide nanoparticles obtained in example 1.
FIG. 5 is a comparison of IR spectra of subminiature magnetic ferroferric oxide nanoparticles obtained in example 1 with that of ethylene glycol.
Fig. 6 is a Transmission Electron Microscope (TEM) image of the ultra-small magnetic ferriferrous oxide nanoparticles obtained in example 2.
FIG. 7 is a Transmission Electron Microscope (TEM) image of the subminiature magnetic ferroferric oxide nanoparticles obtained in example 3.
FIG. 8 is a Transmission Electron Microscope (TEM) image of the subminiature magnetic ferroferric oxide nanoparticles obtained in example 4.
Fig. 9 is a Transmission Electron Microscope (TEM) image of the ultra-small magnetic ferriferrous oxide nanoparticles obtained in example 5.
FIG. 10 is a Transmission Electron Microscope (TEM) image of the subminiature magnetic ferroferric oxide nanoparticles obtained in example 6.
FIG. 11 is a Transmission Electron Microscope (TEM) image of the subminiature magnetic ferroferric oxide nanoparticles obtained in example 7.
Detailed Description
In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
(1) 5mmol ferric chloride was dissolved in 25mL deionized water in an A beaker.
(2) In a B beaker 15mmol of sodium hydroxide was dissolved in 25mL of deionized water.
(3) The solution in beaker B was added to beaker A with magnetic stirring and stirred for 30 minutes to give brown ferrihydrite precipitate.
(4) And (2) centrifugally separating the ferrihydrite precipitate, washing the precipitate with deionized water and absolute ethyl alcohol once respectively, pouring out supernatant, uniformly mixing the supernatant with 50mL of ethylene glycol, transferring the mixture into a 250mL three-neck round-bottom flask, heating the mixture to boiling, keeping the boiling reflux for 12 hours, stopping reaction, and cooling the mixture to room temperature to obtain the reaction solution containing the subminiature magnetic ferroferric oxide nanoparticles. And performing solid-liquid separation to obtain the subminiature magnetic ferroferric oxide nano particles.
Fig. 1 shows an X-ray diffraction pattern (XRD) of the ferrihydrite obtained in this example, from which it can be seen that the obtained product has two very broad diffraction peaks at 34.24 ° and 61.22 °, consistent with 2-line ferrihydrite. Fig. 2 is a Transmission Electron Microscope (TEM) image of the ultra-small magnetic ferriferrous oxide nanoparticles obtained in this example, which shows that the obtained ferriferrous oxide nanoparticles have a uniform size and an average particle diameter of about 7.1 nm; the inset shows a high-resolution transmission electron microscope (HRTEM) image of the obtained nanoparticles, which shows that the obtained nanoparticles are single crystals and have good crystallinity. Fig. 3 shows an XRD spectrum of the ultra-small ferriferrous oxide nanoparticle obtained in this example, from which it can be seen that all diffraction peaks of the nano-small ferriferrous oxide nanoparticle are consistent with those of ferriferrous oxide standard card (JCPES 65-3017), and no hetero-phase diffraction peak exists. Fig. 4 shows the room temperature magnetization curve of the ferroferric oxide nanoparticles obtained in this example, which shows that the obtained nanoparticles are superparamagnetic and have a high room temperature saturation magnetization of 60 emu/g. Fig. 5 shows an infrared absorption spectrum of the ferroferric oxide nanoparticles obtained in this example, and it can be seen that, compared with an infrared absorption spectrum of ethylene glycol, a large number of ethylene glycol molecules are adsorbed on the surfaces of the nanoparticles, and the nanoparticles are endowed with good water solubility.
Example 2
This example is different from example 1 in that the boiling reflux time in the step (4) was 30 minutes. The other process steps are the same as in example 1.
Fig. 6 is a Transmission Electron Microscope (TEM) image of the ultra-small magnetic ferriferrous oxide nanoparticles obtained in this example, which shows that the obtained ferriferrous oxide nanoparticles have a uniform size and an average particle diameter of about 2.5 nm.
Example 3
This example is different from example 1 in that the boiling reflux time in the step (4) is 1 hour. The other process steps are the same as in example 1.
Fig. 7 shows a Transmission Electron Microscope (TEM) image of the ultra-small magnetic ferriferrous oxide nanoparticles obtained in this example, which shows that the obtained ferriferrous oxide nanoparticles have a uniform size and an average particle diameter of about 3.8 nm.
Example 4
This example is different from example 1 in that the boiling reflux time in the step (4) was 2 hours. The other process steps are the same as in example 1.
Fig. 8 is a Transmission Electron Microscope (TEM) image of the subminiature magnetic ferriferrous oxide nanoparticles obtained in this example, which shows that the obtained ferriferrous oxide nanoparticles have a uniform size and an average particle diameter of about 4.9 nm.
Example 5
This example is different from example 1 in that the boiling reflux time in the step (4) was 3 hours. The other process steps are the same as in example 1.
Fig. 9 is a Transmission Electron Microscope (TEM) image of the subminiature magnetic ferriferrous oxide nanoparticles obtained in this example, which shows that the obtained ferriferrous oxide nanoparticles have a uniform size and an average particle diameter of about 6.1 nm.
Example 6
This example is different from example 1 in that the boiling reflux time in the step (4) was 4 hours. The other process steps are the same as in example 1.
Fig. 10 is a Transmission Electron Microscope (TEM) image of the subminiature magnetic ferriferrous oxide nanoparticles obtained in this example, which shows that the obtained ferriferrous oxide nanoparticles have a uniform size and an average particle diameter of about 7.0 nm.
Example 7
This example is different from example 1 in that the boiling reflux time in the step (4) was 8 hours. The other process steps are the same as in example 1.
Fig. 11 is a Transmission Electron Microscope (TEM) image of the subminiature magnetic ferriferrous oxide nanoparticles obtained in this example, which shows that the obtained ferriferrous oxide nanoparticles have a uniform size and an average particle diameter of about 7.1 nm.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (3)
1. A preparation method of subminiature magnetic ferroferric oxide nanoparticles is characterized by comprising the following steps:
(1) ferric salt and alkaline substances are reacted in aqueous solution to obtain ferrihydrite precipitate;
(2) uniformly mixing the ferrihydrite precipitate obtained in the step (1) with polyhydric alcohol, and heating to obtain subminiature magnetic ferroferric oxide nanoparticles; the heating temperature is 130 ℃ to the boiling point of the solution, and the heating time is 10 minutes to 24 hours;
the average grain diameter of the subminiature magnetic ferroferric oxide nano particles is less than 8 nm.
2. The method for preparing the subminiature magnetic ferroferric oxide nanoparticles according to claim 1, wherein the ferric salt in step (1) is any one of ferric chloride, ferric nitrate and ferric sulfate; the alkaline substance is any one of sodium hydroxide, potassium hydroxide, ammonia water, ammonia gas, sodium carbonate, sodium bicarbonate and sodium acetate.
3. The method for preparing subminiature magnetic ferroferric oxide nanoparticles according to claim 1, wherein the polyol in step (2) is any one of ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a molecular weight of less than 1000 daltons, or a mixture thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011538513.XA CN112661195B (en) | 2020-12-23 | 2020-12-23 | Preparation method of subminiature magnetic ferroferric oxide nanoparticles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011538513.XA CN112661195B (en) | 2020-12-23 | 2020-12-23 | Preparation method of subminiature magnetic ferroferric oxide nanoparticles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112661195A CN112661195A (en) | 2021-04-16 |
| CN112661195B true CN112661195B (en) | 2022-09-27 |
Family
ID=75408468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011538513.XA Active CN112661195B (en) | 2020-12-23 | 2020-12-23 | Preparation method of subminiature magnetic ferroferric oxide nanoparticles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112661195B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116313230B (en) * | 2023-02-28 | 2024-06-18 | 重庆大学 | Surface-modified ferroferric oxide nano sieve, preparation method thereof and application thereof in improving breakdown strength of natural ester insulating oil |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008110889A (en) * | 2006-10-30 | 2008-05-15 | Hitachi Maxell Ltd | Method for production of ferric oxide particle |
| CN102515283A (en) * | 2011-12-08 | 2012-06-27 | 桂林理工大学 | Preparation method of magnetic iron oxide nanoparticle capable of stably dispersing in water |
| CN103723773B (en) * | 2012-10-16 | 2016-06-29 | 国家纳米科学中心 | A kind of hydrosol of ferroferric oxide nano granules and its preparation method and application |
| CN103274478A (en) * | 2013-06-15 | 2013-09-04 | 厦门大学 | Method for preparing water-soluble ferroferric oxide nano particle |
| CN107827164A (en) * | 2017-09-30 | 2018-03-23 | 清华大学 | The preparation method of the ferroferric oxide nano granules of the high yield thermal efficiency under a kind of magnetic field |
| CN111517370A (en) * | 2019-02-01 | 2020-08-11 | 中国石油天然气股份有限公司 | Preparation method of magnetic ferroferric oxide nanoparticles |
-
2020
- 2020-12-23 CN CN202011538513.XA patent/CN112661195B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112661195A (en) | 2021-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Esmaeili et al. | Modified single-phase hematite nanoparticles via a facile approach for large-scale synthesis | |
| Huixia et al. | Preparation and characterization of the cobalt ferrite nano-particles by reverse coprecipitation | |
| US20110318261A1 (en) | Preparation Method of Ferroferric Oxide Magnetic Nanospheres | |
| Pérez-Mirabet et al. | One-pot synthesis of stable colloidal solutions of MFe2O4 nanoparticles using oleylamine as solvent and stabilizer | |
| CN102936050B (en) | Preparation method of ferroferric oxide nano sheet | |
| CN106542586B (en) | A kind of preparation method of wolframic acid cobalt nanorod | |
| Di et al. | Influence of precursor Bi3+/Fe3+ ion concentration on hydrothermal synthesis of BiFeO3 crystallites | |
| CN107628648A (en) | A kind of preparation method of pattern and the controllable ferric oxide particles of size | |
| Wang et al. | Synthesis of Co3O4 nanorod bunches from a single precursor Co (CO3) 0.35 Cl0. 20 (OH) 1.10 | |
| CN103274478A (en) | Method for preparing water-soluble ferroferric oxide nano particle | |
| CN112125344B (en) | Preparation method of monodisperse nano iron oxide dispersoid | |
| CN112661195B (en) | Preparation method of subminiature magnetic ferroferric oxide nanoparticles | |
| Wu et al. | Low temperature synthesis of Fe3O4 nanocrystals by hydrothermal decomposition of a metallorganic molecular precursor | |
| CN111517370A (en) | Preparation method of magnetic ferroferric oxide nanoparticles | |
| CN110550666B (en) | Monodisperse and superparamagnetic ferroferric oxide nanoflower and preparation method thereof | |
| CN112408495A (en) | Preparation method of superparamagnetic Ag/ferroferric oxide nanospheres | |
| CN102992408B (en) | Preparation method of ferroferric oxide magnetic nanocrystal | |
| Zhang et al. | A green hydrothermal route to GaOOH nanorods | |
| KR20100016887A (en) | Manufacturing method of nano zinc oxide powders by hydrothermal method | |
| CN102583567B (en) | Superfine high-dispersion super-paramagnetism ferrate nano particles and preparation method thereof | |
| CN104925870A (en) | Solvothermal method for preparing nano-grade ferroferric oxide | |
| Zheng et al. | Environmentally compatible synthesis of superparamagnetic magnetite (Fe3O4) nanoparticles with prehydrolysate from corn stover | |
| Yang et al. | Novel Fe3O4 hollow microspheres: Nontemplate hydrothermal synthesis, superparamagnetism and biocompatibility | |
| Özdinçer et al. | Magnetic spinel-type CoFe2O4 nanoparticles: synthesis and investigation of structural, morphological properties | |
| CN115448374B (en) | Preparation method of magnetic nano particles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |